Process for making high-performance polyethylene multifilament yarn

ABSTRACT

Processes for making high-performance polyethylene multi-filament yarn are disclosed which include the steps of a) making a solution of ultra-high molar mass polyethylene in a solvent; b) spinning of the solution through a spinplate containing at least 5 spinholes into an air-gap to form fluid filaments, while applying a draw ratio DRfluid; c) cooling the fluid filaments to form solvent-containing gel filaments; d) removing at least partly the solvent from the filaments; and e) drawing the filaments in at least one step before, during and/or after said solvent removing, while applying a draw ratio DRsolid of at least 4, wherein in step b) each spinhole comprises a contraction zone of specific dimension and a downstream zone of diameter Dn and length Dn with Ln/Dn of from 0 to at most 25, to result in a draw ratio DRfluid=DRsp*DRag of at least 150, wherein DRsp is the draw ratio in the spinholes and DRag is the draw ratio in the air-gap, with DRsp being greater than 1 and DRag at least 1. High-performance polyethylene multifilament yarn, and semi-finished or end-use products containing said yarn, especially to ropes and ballistic-resistant composites, are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of commonly owned copending U.S.application Ser. No. 15/672,190, filed Aug. 8, 2017, which is acontinuation of U.S. application Ser. No. 14/635,993, filed Mar. 2, 2015(now U.S. Pat. No. 9,759,525), which is a divisional of Ser. No.14/012,413, filed Aug. 28, 2013 (now U.S. Pat. No. 8,999,866), which isa divisional of Ser. No. 12/576,239, filed Oct. 8, 2009 (now abandoned),which is a divisional of Ser. No. 10/584,285, filed Sep. 8, 2006 (nowU.S. Pat. No. 7,618,706), which is the national phase application under35 USC § 371 of PCT/NL2004/000903, filed Dec. 23, 2004, and claims thebenefit of priority of PCT/NL04/00029, filed Jan. 1, 2004, the entirecontents of which are hereby incorporated by reference.

FIELD

The invention relates to a continuous process for makinghigh-performance polyethylene (HPPE) multifilament yarn comprising thesteps of

a) making a 3-25 mass % solution of ultra-high molar mass polyethylenehaving an intrinsic viscosity as measured on solutions in decalin at135° C. of between about 8 and 40 dl/g, in a solvent;b) spinning of the solution through a spinplate containing at least 5spinholes into an air-gap to form fluid filaments, while applying a drawratio DR_(fluid);c) cooling the fluid filaments to form solvent-containing gel filaments;d) removing at least partly the solvent from the filaments; ande) drawing the filaments in at least one step before, during and/orafter said solvent removing, while applying a draw ratio DR_(solid) ofat least 4.

The invention further relates to a high-performance polyethylenemultifilament yarn, and to semi-finished or end-use products containingsaid yarn, especially to various kinds of ropes and ballistic-resistantcomposites.

BACKGROUND AND SUMMARY

Such a process is known from WO 01/73173 A1. A polyethylenemultifilament yarn with a tensile strength of 4.0 GPa for a yarncontaining 60 filaments is described in this patent publication, whichwas made by a continuous process comprising the steps of

a) making a solution of 8 mass % of ultra-high molar mass polyethylenehomopolymer having an intrinsic viscosity of 27 dl/g in mineral oil;b) spinning of the solution through a spinplate containing 60 spinholes,each having a tapered inflow zone of unspecified dimension and adownstream zone of about 1 mm diameter and length/diameter ratio (L/D)of 40, into an air-gap of about 3.2 mm to form fluid filaments, whileapplying a draw ratio DR_(fluid) of 15;c) cooling the fluid filaments in a water quench bath to formsolvent-containing gel filaments;d) removing the solvent from the filaments by extraction withtrichlorotrifluoroethane; ande) drawing the filaments in five steps before, during and after removingthe solvent applying a draw ratio DR_(solid) of 36.5.

A high-performance polyethylene multifilament yarn is herein understoodto mean a yarn containing at least 5 filaments made from ultra-highmolar mass, or ultra-high molecular weight, polyethylene having anintrinsic viscosity (IV, as measured on solutions in decalin at 135° C.)of at least about 4 dl/g (UHPE), the yarn having a tensile strength ofat least 3.0 GPa and a tensile modulus of at least 100 GPa (hereinafteralso simply referred to as strength or modulus). Such HPPE yarns have aproperties profile that make them an interesting material for use invarious semi-finished and end-use products, like ropes and cords,mooring lines, fishing nets, sports equipment, medical applications, andballistic-resistant composites.

Within the context of the present invention a yarn is understood to bean elongate body comprising multiple individual filaments havingcross-sectional dimensions much smaller than their length. The filamentsare understood to be continuous filaments; that is being of virtuallyindefinite length. The filaments may have cross-sections of variousgeometrical or irregular shapes. Filaments within a yarn may be parallelor entangled to one another; the yarn may be linear, twisted orotherwise departed from a linear configuration.

It is well known in the field of fibres and yarn technology that amultifilament yarn shows lower tenacity or tensile strength than thestrength as measured on its constituent individual filaments. Ingeneral, the more filaments a yarn contains, the lower its tensilestrength (breaking strength per unit of cross-sectional area, e.g. N/m²or Pa).

FIG. 1 confirms the said decrease in tensile strength with increasingnumber of filaments in a yarn for some commercially available HPPEyarns; by showing tensile strength (TS) data for the indicated Spectra®and Dyneema® grades, as collected from brochures and web-sites of therespective producers and plotted versus the logarithm of the number offilaments (n) in the yarn. It is thus concluded that the strength of amultifilament yarn is always lower than that of its individualfilaments.

It is furthermore well known, that spinning of high-strengthmultifilament yarn becomes increasingly difficult the higher the numberof filaments in the yarn as spun, one of the likely reasons beingdifferences in spinning and drawing conditions, and subsequently inproperties, occurring between filaments. For a polyethylenemultifilament yarn spinning process to be commercially viable onindustrial scale, it is important that such process can be runcontinuously without interruptions and with high throughput rate, with ahigh number of filaments in the as-spun yarn.

In many of the above-mentioned applications, critical properties of HPPEyarn determining performance in use include tensile properties and creepbehaviour. There is thus a constant need in industry for HPPEmultifilament yarn showing improved performance, like improved tensileproperties. Although various studies suggest the theoretical strength ofa UHPE filament to be in the range 10-20 GPa, the strongest yarnsavailable show much lower strength; for example a 780-filament Dyneema®SK75 yarn has a strength of about 3.5 GPa. More specifically therefore,there is a need for a process that enables production of such highertensile strength yarn on industrial scale.

According to the present invention, this is provided by a process

wherein in step b) each spinhole comprises a contraction zone with agradual decrease in diameter from D₀ to D_(n) with a cone angle in therange 8-75°, and wherein the spinhole comprises a zone downstream of thecontraction zone of constant diameter D_(n) with a length/diameter ratioL_(n)/D_(n) of from 0 to at most 25, to result in a fluid draw ratioDR_(fluid)=DR_(sp)*DR_(ag) of at least 150, wherein DR_(sp) is the drawratio in the spinholes and DR_(ag) is the draw ratio in the air-gap,with DR_(sp) being greater than 1 and DR_(ag) at least 1.

With the process according to the invention a HPPE multifilament yarncan be obtained that has higher tensile strength than any known HPPEyarn containing at least 5 filaments, especially an as-spun yarn; morespecifically a HPPE multifilament yarn containing n filaments has andhaving a tensile strength TS obeying the formula TS≥f*(n^(−0.065)) GPa,wherein factor f is at least 5.8 and n is at least 5.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is is a plot of tensile strength (TS) versus the number offilaments (n) for some commercially available HPPE yarns, i.e., Spectra®brand and Dyneema® brand yarns;

FIG. 2 is a plot of TS versus the number of filaments in a yarn forExamples 1-20 I comparison to Comparative Experiments A-H and the datafor the commercially available HPPE yarns of FIG. 1;

FIG. 3 is a plot of V50 values (m/s) versus areal density of panels madewith the yarns of Examples 21-23 in comparison to Comp. ex. K; and

FIG. 4 is a plot of V50 values (m/s) versus areal density of panels madewith the yarns of Examples 24-26 in comparison to Comp. exp. L.

DETAILED DESCRIPTION

It is surprising that the process according to the invention results inyarn with improved tensile properties, because processes for making HPPEmultifilament yarn comprising a step with a certain draw ratio, alsoreferred to as stretch ratio, applied to filaments in the solution orfluid state (DR_(fluid)) have already been described in numerouspublications. For example, in EP 0472114 B1 a process is disclosed,wherein a minimum draw ratio DR_(fluid) of at least 3 is applied in anair-gap of several centimetres. For making 16- or 19-filament yarn frompolyethylene of intermediate molar mass (preferably 300-700 kg/mol) aDR_(fluid) of 10-50 is indicated as a preferred range for reachingoptimum properties. EP 0200547 B1 suggests that the optimum DR_(fluid)lies in the range from 6 to 200, depending on the concentration of thesolution and operating conditions. This publication, however, onlydiscloses spinning of a monofilament in its examples. In EP 0064167 A1it is concluded, based on a very large number of experiments, thatdrawing in the air-gap should be minimized, because substantialstretching would be highly detrimental. In addition, EP 0064167 A1 alsounambiguously teaches that a long straight capillary is to be preferredover a conical spinhole for increasing polyethylene filament strength.In WO 01/73173 A1 it is indicated that the draw ratio DR_(fluid) ispreferably at least 12; but a 16-filament yarn made with a DR_(fluid) ofabout 34 had tensile properties lower than a yarn made with a DR_(fluid)of about 23. None of these publications discloses or suggests applying aminimum draw ratio DR_(fluid) of 150, resulting from drawing in both thespinhole (by applying a specific spinhole geometry) and the air-gap tomake a multifilament yarn with higher strength.

Another advantage of the process according to the invention is that thedraw ratio DR_(sp) can be set by choosing the geometry of the spinholes,which can be much better controlled than drawing in an air-gap. Afurther advantage is that the temperature during drawing in thespinholes can be better controlled than in the air-gap, which furtherreduces differences in processing conditions between filaments and withtime. It is known that even small differences in the temperature of apolyethylene solution will strongly affect its rheological properties,and thus drawing behaviour. Still a further advantage is that a largerair-gap can be applied, which is less critical to small fluctuations,for example resulting from movement of the surface of the quench bath. Adistinct advantage of the process of the invention is thus an improvedprocessing stability, and more consistency in properties between andalong filaments. These advantages become more apparent with increasingnumber of filaments that are being spun. Preferably, the number offilaments in the yarn is at least 10, 50, 100, 150, 200, 300, 375 oreven at least 450. For practical reasons, handling during spinning anddrawing becoming increasingly difficult, the number of filaments ispreferably at most about 5000.

A spinplate is also called spinneret in the art, and contains multiplespinholes, also called orifices, dies, apertures, capillaries orchannels. The number of spinholes determines the maximum number offilaments in as-spun yarn. The spinhole has certain geometry in lengthand transverse directions, and is preferably of circular cross-sectionto result in highest strength, but also other shapes are possible, ifother forms of filaments are desired. Within the context of the presentinvention the diameter is meant to be the effective diameter; that isfor non-circular or irregularly shaped spinholes the largest distancebetween an imaginary line connecting the outer boundaries.

Within the context of the present invention, a draw ratio of greaterthan 1 in a spinhole is applied, if the polyethylene chains in thesolution are oriented as a result of an elongational flow field in thespinhole and the orientation so obtained is not subsequentlysubstantially lost as a result of relaxation processes (occurring in thespinhole). Such molecular orientation, and thus a draw ratio greaterthan 1 results if the solution flows through a spinhole having ageometry comprising a contraction zone, more specifically in the processaccording to the invention a zone with a gradual decrease in diameterfrom diameter D₀ to D_(n) with a cone angle in the range 8-75°, andoptionally comprising a zone of constant diameter D_(n) downstream of acontraction zone, with a length/diameter ratio L_(n)/D_(n) of at most25. Downstream is understood to mean after the contraction zone in thedirection of the flowing solution, that is more to the exit side of thespinplate. If the length of a zone with constant diameter is above25D_(n), molecular orientation introduced in the contraction zone wouldbe substantially lost again; that is there would be no effectiveorientation or drawing. The draw ratio in such case is defined asDR_(sp)=1.

With cone angle is meant the maximum angle between the tangents ofopposite wall surfaces in the contraction zone. For example, for aconical or tapered contraction the angle between the tangents is aconstant, i.e. the cone angle; for a so-called trumpet type ofcontraction zone the angle between the tangents will decrease withdecreasing diameter; whereas for a wineglass type of contraction zonethe angle between the tangents will pass through a maximum value.

A higher cone angle induces more elongational flow, but if the coneangle is greater than 75° flow instabilities like turbulence may disturbthe desired elongational orientation of the molecules. Preferably, thecone angle is therefore at most 70°, at most 65°, at most 60°, at most50°, more preferably at most 45°. With decreasing cone angle orientingthe polymer molecules becomes less effective, and very small angleswould result in very long spinholes. Preferably, the cone angle is thusfrom at least 10, more preferably at least 12°, or even at least 15°.

The draw ratio in the spinhole is represented by the ratio of thesolution flow speeds at the initial diameter or cross-section and thefinal diameter of the spinhole; which is equivalent to the ratio of therespective cross-sectional areas, or the ratio between the square of theinitial and final diameters in case of cylindrical holes, that isDR_(sp)=(D₀/D_(n))².

Preferably, the draw ratio in the spinholes is at least 2, 5, 10, 15,20, 25, 30, 35, 40, 45 or even at least 50, because extent andconditions of drawing can be well controlled in the spinholes. Inaddition, a higher draw ratio in the spinhole, with constant draw ratioin the air-gap, has been found to result in higher tensile strength ofthe yarn obtained. In a special embodiment, the DR_(sp) is larger thanDR_(ag) for the same reason.

The spinhole further comprises a zone of constant diameter D_(n)downstream of a contraction zone, this zone having a length/diameterratio L_(n)/D_(n) of at most 25. The length of this zone can also be 0;such a zone need not be present in the spinhole. The advantage of thepresence of this constant diameter zone is a further improved stabilityof the spinning process. On the other hand, its length should be limitedin order that the molecular orientation introduced in the contractionzone is not substantially lost. Therefore, the ratio L_(n)/D_(n) ispreferably at most 20, at most 15, 10, or even at most 5.

The final diameter of the spinhole may vary considerably, depending ontotal draw ratio applied in the process and desired final filamentthickness. A suitable range is from 0.2 to 5 mm, preferably the finaldiameter is from 0.3 to 2 mm.

The spinholes may also contain more than one contraction zone, eachoptionally followed by a zone of constant diameter. In such case similarfeatures relate to each zone as discussed above.

In a special embodiment of the process according to the invention, thespinholes in the spinplate further comprise an inflow zone of constantdiameter of at least D₀, and of length L₀ with a ratio L₀/D₀ of at least5. The advantage of such zone is that the polymer molecules in thesolution can at least partly relax before entering the contraction zone,such that pre-orientation originating from flow fields further upstreamin the process will disappear or at least significantly diminish. Thisis especially advantageous in case of a high number of spinholes,requiring complex feed channels to the spinplate, which may result inquite different flow histories and degrees of pre-orientation perspinhole; and thus in differences in drawing behaviour of filaments, andin differences in properties between filaments in the yarn. The longerthis inflow zone, the more relaxation can occur, and the better interfilament homogeneity or yarn uniformity. Therefore, the inflow zonepreferably has a L₀/D₀ of at least 10, 15, 20, or even at least 25. Itshould be noted that the flow speed in this zone is significantly lowerthan after passing the contraction zone, and for relaxation to occur arelatively small L₀/D₀ suffices. Above a certain length, furtherincrease has hardly any effect, but such a long inflow zone would resultin very thick spinplates that are more difficult to make and handle. Theinflow zone thus preferably has a L₀/D₀ of at most 100, or at most 75,or 50. The optimum length depends on factors like molar mass ofpolyethylene, concentration of the solution, and flow speeds.

In a preferred embodiment of the process according to the invention aspinplate comprising at least 10 cylindrical spinholes having a inflowzone of constant diameter D₀ with L₀/D₀ at least 10, at least onecontraction zone with cone angle in the range 10-60°, a downstream zoneof constant diameter D_(n) with L_(n)/D_(n) at most 15, and (D₀/D_(n))²of at least 5 is applied, but also any other combination of indicatedpreferred embodiments is possible.

In the process according to the invention the fluid filaments can befurther drawn upon leaving the spinhole, by applying a higher pick-uprate after cooling the filaments, than the flow rate upon leaving thespinhole. This stretching applied before solidification upon cooling iscalled the draw ratio in the air-gap DR_(ag), and is in prior art alsoreferred to as draw down. The DR_(ag) can be 1.0 if the pick-up ratesequals the flow rate, but the draw ratio is preferably greater than 1 tokeep the filaments under sufficient tension and to prevent relaxation.Preferably, DR_(ag) is optimised in combination with the applied DR_(sp)to reach a certain DR_(fluid). Preferably, the draw ratio in the air-gapis at least 2, 5, or 10. The dimension of the air-gap, that is thedistance from the exit of the spinplate to the surface of the quenchbath, appears not to be very critical, although it is preferably keptconstant and the same for all filaments, and can be from some mm toseveral cm. If the air-gap is too long, molecular relaxation processesmay annul part of the orientation obtained. Preferably, the air-gap isof about 5-50 mm length.

The draw ratio DR_(fluid), being DR_(sp)*DR_(ag), that is applied tofluid filaments is at least 150, preferably at least 200, 250, or evenat least 300. It is found that such a high draw ratio applied to fluidfilaments results in improved drawability of the gel and dried filaments(DR_(solid)), and/or in improved properties, like tensile strength ofthe resulting yarn. This is also synonymous with improved processingstability of the process, since it reduces the chance that a filament isover-stressed during (semi-)solid state drawing at a certain draw ratioclosely below the maximum, and thus reduces frequency of filamentbreakage. This is a surprising result, since experiments in prior artpublications like EP 0064167 A1 or WO 01/73173 A1 indicate thatincreasing the DR_(fluid) results in a lower draw ratio that cansubsequently be applied to the solid filaments, and in lower tensileproperties of the yarn.

The ultra-high molar mass polyethylene applied in the process accordingto the invention has an intrinsic viscosity (IV, as measured on solutionin decalin at 135° C.) of between about 8 and 40 dl/g, preferablybetween 10 and 30, or 12 and 28, more preferably between 15 and 25 dl/g,to provide a balance between processability of the solution to be spunand mechanical properties of the obtained filaments. Intrinsic viscosityis a measure for molar mass (also called molecular weight) that can moreeasily be determined than actual molar mass parameters like M_(n) andM_(w). There are several empirical relations between IV and M_(w), butsuch relation is dependent on molar mass distribution. Based on theequation M_(w)=5.37*10⁴ [IV]^(1.37) (see EP 0504954 A1) an IV of 4 or 8dl/g would be equivalent to M_(w) of about 360 or 930 kg/mol,respectively. It is well known that during processing of a polymer atelevated temperature generally some chain scission occurs, leading to alower molar mass of the product obtained versus that of the startingpolymer. It is found that upon gel spinning of UHPE an IV drop of about1-3 g/dl may occur, depending on starting molar mass and processingconditions.

Preferably, the UHPE is a linear polyethylene with less than one branchper 100 carbon atoms, and preferably less than one branch per 300 carbonatoms; a branch or side chain or chain branch usually containing atleast 10 carbon atoms. The linear polyethylene may further contain up to5 mol % of one or more comonomers, such as alkenes like propylene,butene, pentene, 4-methylpentene or octene.

In a preferred embodiment, the UHPE contains a small amount, preferablyat least 0.2, or at least 0.3 per 1000 carbon atoms, of relatively smallgroups as pending side groups, preferably a C1-C4 alkyl group. It isfound that by applying a polymer containing a certain amount of suchgroups results in yarns having an advantageous combination of highstrength and further improved creep behaviour. Too large a side group,or too high an amount of side groups, however, negatively affects theprocessing and especially the drawing behaviour of the filaments. Forthis reason, the UHPE preferably contains methyl or ethyl side groups,more preferably methyl side groups. The amount of side groups ispreferably at most 20, more preferably at most 10, 5 or at most 3 per1000 carbon atoms.

The UHPE that is applied in the process according to the invention mayfurther contain small amounts, generally less than 5 mass %, preferablyless than 3 mass % of customary additives, such as anti-oxidants,thermal stabilizers, colorants, flow promoters, etc. The UHPE can be asingle polymer grade, but also a mixture of two or more differentpolyethylene grades, e.g. differing in IV or molar mass distribution,and/or type and number of comonomers or side groups.

In the process according to the invention any of the known solventssuitable for gel spinning of UHPE can be used as solvent for making thepolyethylene solution, for example paraffin wax, paraffin oil or mineraloil, kerosenes, decalin, tetralin, or a mixture thereof. It is foundthat the present process is especially advantageous for relativelyvolatile solvents, preferably solvents having a boiling point atatmospheric conditions of less than 275° C., more preferably less than250 or 225° C. Suitable examples include decalin, tetralin, and severalkerosene grades. The solution of UHPE in solvent can be made using knownmethods. Preferably, a twin-screw extruder is applied to make ahomogeneous solution from a UHPE/solvent slurry. The solution ispreferably fed to the spinplate at constant flow rate with meteringpumps. The concentration of the UHPE solution is between 3 and 25 mass%, with a lower concentration being preferred the higher the molar massof the polyethylene is. Preferably, the concentration is between 3 and15 mass % for UHPE with IV in the range 15-25 dl/g.

The UHPE solution is preferably of substantially constant compositionover time, because this further improves processing stability andresults in yarn of more constant quality over time. With substantiallyconstant composition it is meant that parameters like UHPE chemicalcomposition and molar mass, and concentration of UHPE in the solutionvary only within a certain range around a chosen value.

Cooling of the fluid filaments into solvent-containing gel filaments maybe performed with a gas flow, or by quenching the filament in a liquidcooling bath after passing an air-gap, the bath preferably containing anon-solvent for the UHPE solution. If gas cooling is applied, theair-gap is the length in air before the filaments are solidified.Preferably a liquid quench-bath is applied in combination with anair-gap, the advantage being that drawing conditions are better definedand controlled than by gas cooling. Although called air-gap, theatmosphere can be different than air; e.g. as a result of an inert gaslike nitrogen flowing, or as a result of solvent evaporating fromfilaments. Preferable, there is no forced gas flow, or only of low flowrate. In a preferred embodiment, the filaments are quenched in a bathcontaining a cooling liquid, which liquid is not miscible with thesolvent, the temperature of which is controlled, and which flows alongthe filaments at least at the location where the fluid filaments enterthe quench bath.

Solvent removal can be performed by known methods, for example byevaporating a relatively volatile solvent, by using an extractionliquid, or by a combination of both methods.

The process for making a polyethylene yarn according to the inventionfurther comprises, in addition to drawing the solution filaments,drawing the filaments in at least one drawing step performed on thesemi-solid or gel filaments and/or on solid filaments after cooling andat least partial removal of solvent, with a draw ratio of at least 4.Preferably, drawing is performed in more than two steps, and preferablyat different temperatures with an increasing profile between about 120and 155° C. A 3-step draw ratio applied on (semi-) solid filaments isrepresented as DR_(solid)=DR_(solid 1)*DR_(solid 2)*DR_(solid 3); i.e.it is composed of the draw ratios applied in each drawing step.

It is found that a draw ratio DR_(solid) of up to about 35 can beapplied, to reach the highest tensile properties of the yarn obtainablefor a given DR_(fluid). As a result of improved drawability and strengthof partly drawn filaments in the process according to the invention,relatively high draw ratios, preferably in the range 5-30, may beapplied without frequent filament breakage occurring, also depending onthe applied draw ratio on fluid filaments. The process according to theinvention thus results in multifilament HPPE yarn not only showinghigher tensile strength than known multifilament yarns, but also lessfluffing (resulting from the presence of broken filaments); especiallyif draw ratios have been optimised.

In a special embodiment according to the invention, a 3-15 mass %solution of linear UHPE of IV 15-25 dl/g is spun through a spinplatecontaining at least 10 spinholes into an air-gap, the spinholescomprising at least one contraction zone with a cone angle in the range10-60° and comprising a zone of constant diameter D_(n) with alength/diameter ratio L_(n)/D_(n) smaller than 10 downstream of thecontraction zone, while applying a fluid draw ratioDR_(fluid)=DR_(sp)*DR_(ag) of at least 200 and a draw ratio DR_(solid)of between 5 and 30; but also other combinations of said parametersettings provide good results.

The process according to the invention may further comprise additionalsteps known in the art, like for example applying a spin finish orsizing agent to the yarn.

The invention further relates to a spinplate comprising at least 5spinholes of geometry and preferred features as defined and describedabove. The advantage of said spinplate is that, when applied in aprocess for making high-performance polyethylene multifilament yarn itenables a high degree of drawing on fluid filaments and a stablespinning process, resulting in yarn of increased strength and with highconsistency in properties between individual filaments.

The invention further relates to a HPPE multifilament yarn that isobtainable by the process according to the invention, the yarn showinghigher tensile strength than any known HPPE yarn containing at least 5filaments. More specifically, the invention relates to a HPPEmultifilament yarn made from linear UHPE of IV 8-40 dl/g, containing nfilaments and having a tensile strength of at least f*(n^(−0.065)N) GPa,wherein factor f is at least 5.8 and n is at least 5. Preferredembodiments of the yarn according to the invention are based on UHPEgrades as described above. Preferably, the yarn has a tensile strengthobeying said formula wherein f is at least 6.0, 6.2 or even at least6.4. Considering that the maximum theoretical strength of a filament isby some authors indicated to be about 10 GPa, factor f would be 10 atmost, or even at most 9 or 8.

The HPPE multifilament yarn according to the invention is furthercharacterized by a total enthalpy of non-reversible transitions asmeasured by temperature-modulated differential scanning calorimetry(TMDSC) of at least 200 J/g. In addition, or alternatively, the HPPEmultifilament yarn according to the invention is further characterizedby a peak in the non-reversible TMDSC curve, called hereafternon-reversible peak, with a maximum at about 152° C. as measured byTMDSC having an enthalpy of at least 35 J/g, preferably at least 38 or40 J/g. Although these TMDSC results are not yet fully understood andthe inventors do not wish to be bound to any theory, it is presentlybelieved that especially the non-reversible peak at 152° C. correlatesto oriented crystallisation of the polyethylene molecules promoted bythe spinning process of the invention, and resulting in improvedmechanical properties.

The HPPE multifilament yarn according to the invention is further foundto show favourable creep resistance, for example expressed in a creeprate as determined on yarn at 70° C. with a load of 600 MPa of at most5*10⁻⁶ s⁻¹, preferably at most 4*10⁻⁶ s⁻¹. A HPPE multifilament yarnaccording to the invention made from a linear UHPE with 0.2-10 C1-C4alkyl groups per 1000 C atoms shows even better resistance to creep incombination with high strength; that is it has a creep rate asdetermined on yarn at 70° C. with a load of 600 MPa of at most 3*10⁻⁶s⁻¹, preferably at most 2*10⁻⁶ s⁻¹ or even 1*10⁻6 s⁻¹.

Preferably, the number of filaments in the yarn according to theinvention is at least 10, 50, 100, 150, 200, 300, 375 or even at least450.

Preferably, the said yarn is an as-spun or as-produced yarn; meaning theyarn is the direct product of a spinning and drawing process, and is notmade by assembling separately produced yarns containing less filaments.Of course, the as-produced yarn according to the invention can furtherbe assembled into yarns, or ropes etc, of higher titer or lineardensity.

Such high-strength yarn is very useful for various applications, likemaking of heavy-duty ropes and cables, or for making ballistic-resistantcomposites offering improved protection level, or reduced weight. Yarnof relatively low titer, containing for example from 5 to 300 filaments,but of extremely high strength is a.o. very suited for makinghigh-strength surgical sutures and cables, or other medical implants.For medical applications the amount of other components or foreignmaterials in the yarn is very important, in addition to its mechanicalproperties. The invention therefore also specifically relates to a HPPEmultifilament yarn according to the invention containing less than 150ppm of residual solvent, specifically of solvent having a boiling pointat atmospheric conditions of less than 275° C., preferably containingless than 100, 75, or even less than 50 ppm of solvent, and to medicalimplants containing such yarn.

The invention specifically relates to a HPPE multifilament yarncontaining at least 20 filaments, the yarn being made from UHPE of IV8-40 dl/g and having a tensile strength of at least f*(n^(−0.065)N) GPa,with n at least 20 and f at least 5.8. Especially for making ropes,multifilament yarn of such high strength, which also shows an elongationat break of more than about 2.5% is advantageous, because of higherstrength efficiency of such ropes. The invention therefore specificallyrelates to a HPPE multifilament yarn containing at least n filamentsmade from UHPE of IV 8-40 dl/g, which yarn has a tensile strength of atleast f*(n^(−0.065)N) GPa with n at least 200, preferably at least 300or 375 and with f at least 5.8, a creep rate as determined at 70° C.with a load of 600 MPa of at most 5*10⁻⁶ s⁻¹, and an elongation at breakof at least 2.8%.

The invention further relates to various semi-finished and end-usearticles containing the high-performance polyethylene multi-filamentyarn according to the invention, or a high-performance polyethylenemulti-filament yarn obtainable by the process according to theinvention. Examples of such articles include various ropes and cords,fishing nets, sports equipment, medical implants like suture and cables,and ballistic-resistant composites. In most of these applications thetensile strength of the yarn is an essential parameter determiningperformance of the article.

Ropes especially include heavy-duty ropes for application in marine andoffshore operations, like anchor handling, seismic operations, mooringof drilling rigs and production platforms, and towing. Preferably, suchropes contain at least 50 mass % of the yarn according to the invention,more preferably at least 75, or even 90 mass %. Most preferably, therope consists essentially of HPPE yarn according to the invention. Suchproducts also show improved performance, like reduced creep and longertime to rupture under continuous loading conditions, in addition tohigher strength. Products containing high amounts of HPPE yarn have alow relative density; possibly lower than water, which is an advantagein marine and offshore applications.

The invention further relates to a multi-layer ballistic-resistantassembly containing a plurality of mono-layers comprising HPPE yarnaccording to the invention, and to ballistic-resistant articlescomprising such an assembly. The HPPE yarn can be present in variousforms in a mono-layer, including woven and non-woven fabrics.Preferably, the mono-layers contain uni-directionally oriented HPPEfilaments; with the fibre direction in each mono-layer being rotatedwith respect to the fibre direction in an adjacent mono-layer. Themono-layers may further comprise a binder material, basically to holdthe filaments together. The binder material can have been applied byvarious techniques; for example as a film, as a transverse bonding stripor fibres (transverse with respect to the uni-directional filaments), orby impregnating and/or embedding the filaments with a matrix, e.g. witha solution or dispersion of matrix material in a liquid. The amount ofbinder material is preferably less than 30 mass % based on the mass ofthe layer, more preferably less than 20 or 15 mass %. The mono-layersmay further comprise small amounts of auxiliary components, and maycomprise other filaments. Preferably the mono-layers only comprise HPPEfilaments as reinforcing fibres. Such mono-layers are therefore alsoreferred to as mono-layers consisting essentially of HPPE filaments.

The multi-layer ballistic-resistant assembly can also be an assembly ofat least two preformed sheet layers, a sheet layer comprising at leasttwo mono-layers comprising high-performance fibres and a bindermaterial, and optionally other layers, like a film or fabric; that havebeen consolidated or attached to each other. Such multi-layerballistic-resistant assemblies or panels, and their manufacture areknown in the art, for example from U.S. Pat. Nos. 4,916,000, 4,623,574,EP 0705162 A1 or EP 0833742 A1.

For so-called hard ballistic applications like vehicle armouring, rigidpanels that have been (compression-) moulded from a plurality ofmono-layers containing HPPE yarn are generally applied. For softballistic applications like body armour, flexible panels assembled froma plurality of mono-layers containing HPPE yarn, e.g. by stackingmono-layers or preformed sheets and securing the stack by for examplestitching at the corners or around the edges, or by placing inside anenvelope, are preferred.

A multi-layer ballistic-resistant assembly containing mono-layersconsisting essentially of HPPE yarn according to the invention showssurprisingly good anti-ballistic properties, exceeding the performanceof known assemblies or panels. It is for example found that a flexibleassembly that fulfils the NIJ II requirements (stopping of a 9 mmParabellum FMJ (full metal jacket) bullet of 8.0 g with impact speed of367 m/s, and a 0.357 Magnum JSP (jacketed soft point) bullet of 10.2 gat a speed of 436 m/s), has an areal density about 25% or more lowerthan that of a state-of-the-art panel. A reduced weight is a distinctadvantage in both personal protection as in vehicle armouring and thelike.

The invention more specifically relates to a ballistic-resistantassembly comprising a plurality of mono-layers consisting essentially ofHPPE multifilament yarn, the assembly having an areal density (AD) of atleast 1.5 kg/m² and a specific energy absorption (SEA) of at least 300J·m²/kg as measured against a 9*19 mm FMJ Parabellum bullet according toa test procedure based on Stanag 2920. Preferably, the assembly has aSEA of at least 325, or at least 350 J·m²/kg. Areal density is expressedin mass per surface area, and is also referred to as areal mass or arealweight.

The invention further relates to a ballistic-resistant moulded panelcomprising a plurality of mono-layers consisting essentially of HPPEmultifilament yarn, the panel having a specific energy absorption (SEA)of at least 165 J·m²/kg as measured against an AK-47 bullet according toa test procedure based on Stanag 2920. Preferably, the panel has a SEAof at least 170, or at least 175 J·m²/kg.

The invention is further elucidated by the following examples andcomparative experiments.

Methods

-   -   IV: the Intrinsic Viscosity is determined according to method        PTC-179 (Hercules Inc. Rev. Apr. 29, 1982) at 135° C. in        decalin, the dissolution time being 16 hours, with DBPC as        anti-oxidant in an amount of 2 g/I solution, by extrapolating        the viscosity as measured at different concentrations to zero        concentration;    -   Side chains: the number of side chains in a UHPE sample is        determined by FTIR on a 2 mm thick compression moulded film, by        quantifying the absorption at 1375 cm⁻¹ using a calibration        curve based on NMR measurements (as in e.g. EP 0269151);    -   Tensile properties: tensile strength (or strength), tensile        modulus (or modulus) and elongation at break (or eab) are        defined and determined on multifilament yarns with a procedure        in accordance with ASTM D885M, using a nominal gauge length of        the fibre of 500 mm, a crosshead speed of 50%/min and Instron        2714 clamps, of type Fibre Grip D5618C. On the basis of the        measured stress-strain curve the modulus is determined as the        gradient between 0.3 and 1% strain. For calculation of the        modulus and strength, the tensile forces measured are divided by        the titre, as determined by weighing 10 metres of fibre; values        in GPa are calculated assuming a density of 0.97 g/cm³;    -   Temperature Modulated Differential Scanning calorimetry (TMDSC)        experiments were carried out on a TA Instruments Heatflux DSC        2920 equipped with a Refrigerated Cooling System (RCS). Helium        was used as purge gas (35 ml/min). Aluminum crucibles (Perkin        Elmer, robotic pans) were used as sample holders. Fibres were        cut to a length between 1 and 2 mm before analysis. Calibration        procedures included temperature calibration water and Indium;        enthalpy calibration with Indium; and heat capacity calibration        with Standard Reference Material1484 Linear Polyethylene Cp at        150° C.=2.57 J/° C. (National Bureau of Standards Washington        D.C.). The applied measuring conditions are based on a        publication by G. Hohne for UHPE powder (Thermochimica Acta 396,        2003, 97-108). The measuring method included equilibration at        80° C.; modulation +/−0.20° C. every 80 seconds; and scanning at        a rate of 1.00° C./min to 180° C. TMDSC curves for reversible        and non-reversible transitions were calculated from measured        total heat flow and complex heat capacity. Reported values for        peak temperatures and enthalpies of various peaks were        calculated with standard soft-ware assuming a continuous        base-line; for peaks having a (broad) maximum below 140° C., a        maximum in the range 140-144 (142) ° C., and in the range        150-153 (152) ° C.    -   Creep properties of yarns were determined with an experimental        set-up comprising a temperature-controlled chamber, sample        fixations with a cylindrical steel rod having a smooth surface,        and an automated system to load the sample, and to monitor the        displacement of the applied weight versus time. The ends of a        yarn sample of suitable length, from 200-1000 mm depending on        anticipated elongation, is wound several times around the steel        rod and fixated with knots. The sample is then placed in the        creep chamber, and after preloading during 10-30 s and        subsequent relaxation, the measurement is started. The observed        elongation versus time typically shows three regimes: after an        initially relatively fast elongation a plateau in creep rate is        reached (regime 2, also called steady state creep). In the third        regime, molecular chain scission effects start to play a role in        addition to plastic creep, finally resulting in yarn breakage.        The reported creep values relate to regime 2, as calculated from        experiments performed at 70° C. and with 600 MPa load on the        yarn. Creep life time values were determined as the transfer        from regime 2 to regime.    -   Ballistic performance: V50 and SEA of composite panels were        determined at 21° C. with test procedures according to Stanag        2920, using 9 mm*19 mm FMJ Parabellum bullets (from Dynamit        Nobel); Fragment Simulating Projectiles (FSP) of 1.1 gram and        5.38 mm; or 7.62*39 mm AK-47 Mild Steel Core bullets of 8.0 g        (from Conjoy, UK). After conditioning at 21° C. and 65% relative        humidity during at least 16 hours, an assembly of layers was        fixed using flexible straps on a support filled with Roma        Plastilin backing material, which was preconditioned at 35° C.        In case of AK-47 ammunition, panels were clamped onto a steel        frame and fired at without backing.

Examples 1-2

A 6 mass % solution of a UHPE homopolymer having less than 0.3 sidegroups per 1000 per carbon atoms and an IV of 27.0 dl/g in decalin,containing a ratio of cis/trans isomers of between 38/62 and 42/58, wasmade, and extruded with a 25 mm twin screw extruder equipped with agear-pump at a temperature setting of 180° C. through a spinplate having24 spinholes into a nitrogen atmosphere with a rate of 1.0 g/min perhole. The spinholes had an initial cylindrical channel of 3.0 mmdiameter and L/D of 18, followed by a conical contraction with coneangle 45° into a cylindrical channel of 1.0 mm diameter and L/D of 10.The solution filaments were cooled in a water bath kept at about 35° C.and with a water flow rate of about 5 cm/s perpendicular to thefilaments entering the bath, and taken-up at such rate that a draw ratioof 15 was applied to the as-spun filaments in the air-gap of 15 mm. Thefilaments subsequently entered an oven at 130° C. The filaments werefurther stretched by applying a draw ratio of about 4, during whichprocess the decalin evaporated from the filaments. The total draw ratioDR_(overall) (=DR_(fluid)*DR_(solid)) amounted 1440. The yarn thusobtained had a tensile strength of 5.2 GPa and a modulus of 202 GPa.Relevant data is shown in Table 1.

In Example 2 the experiment was repeated, be it that a draw ratio in thesemi-solid state of 5 was applied. As a result of the higher draw ratio,also higher tensile properties were found.

Comparative Experiment A

In this experiment the draw ratio in the air-gap was lowered, resultingin a DR_(fluid) of 135. The measured tensile strength was significantlylower than for higher draw ratio.

Example 3

This experiment is performed analogously to the foregoing, withfollowing modifications: the spinplate has an inflow channel of diameter4.5 mm and L/D=10, a contraction zone with cone angle 20°, andsubsequent channel of diameter 0.3 mm and L/D of 5, resulting in aDR_(sp) of 225; the draw ratio in the air-gap is about 1.01 by matchingtake-up speed with flow speed. With the draw ratio applied to thesolidified filaments set at 5, the resulting yarn shows extremely hightensile strength and modulus.

Comparative Experiments B-C

In these experiments a solution of a UHPE polymer having less than 0.3side groups per 1000 per carbon atoms and an IV of 19.8 dl/g in decalinwas extruded with a 40 mm twin screw extruder equipped with a gear-pumpat a temperature setting of 180° C. through a spinplate having 195spinholes into an air-gap with a rate of 2.2 g/min per hole. Thespinholes had the same geometry as in Ex 1-2, but with cone angle 60°.In exp. B an 8 mass % solution was used, in exp. C 9 mass %. The waterin the quench bath was kept at 30-40° C., and had a flow rate of about 3cm/s near the filaments. Solid-state drawing was performed in two steps,first with a temperature gradient of about 110-140° C. and than at about151° C. The draw ratio in the air-gap could not be increased too muchwithout processing instabilities occurring (filament breakage), unlikein e.g. Ex. 1, which may be related to the lower molar mass UHPE used.The resulting yarn had a strength comparable with known yarns, see Table1 and FIG. 2.

Examples 4-5

The same spinning and drawing equipment and conditions as in Comp. Exp.B-C were used, but with a spinplate having an inflow channel of diameter3.5 mm and L/D=18, a contraction zone with cone angle 60°, andsubsequent channel of diameter 1.0 mm and L/D of 10, resulting in aDR_(sp) of 12.25. The spin rate was 1.7 g/min per hole. The draw ratioin the air-gap could be increased, resulting in stable production ofvery high strength yarn, see Table 1 and FIG. 2.

Example 6

Example 4 was repeated with a spinplate having 195 holes of similargeometry, but with a cone angle of 30°.

Comparative Experiments D-F

Analogously to Comparative experiments B-C a yarn was made, but with aspinplate containing 390 spinholes of same geometry. HDPE solution was8, 8 and 9 mass % respectively. The experimental results were alsohighly comparable; the yarn showing slightly lower tensile strength asexpected for the higher number of filaments.

Examples 7-10 and Comparative Experiment G

Using the same set-up and conditions as in comp. Exp. D, yarns were spunapplying a spinplate having 390 spinholes of geometry as in Ex 4-5. InEx. 10 the spinrate was lowered to 1.7 g/min per hole. Again, a highdraw ratio could be applied to the fluid filaments, resulting in verygood tensile properties; see Table 1 and FIG. 2. If the DM was decreasedby applying a relatively small draw ratio in the air-gap, tensilestrength dropped significantly (Comp. Exp. G).

Examples 11-12

Multifilaments yarns were spun from a decalin solution containing 8 mass% of UHPE of IV 19.8 dl/g, using a 130 mm twin-screw extruder equippedwith a gear-pump through spinplates containing 588 spinholes having aninflow zone of diameter 3.5 mm and L/D of 18, a conical contraction zonewith cone angle 60°, and subsequent capillary with diameter 0.8 mm andL/D 10. The draw ratio in the spinholes was thus 19.1; the draw ratio inthe air-gap was 16.2 and 18.1 (at spinrates 2.2 and 2.0 g/min perspinhole). Water flow rate in the cooling bath was about 6 cm/s. Thetensile properties of the yarns are in agreement with yarns producedunder similar conditions but containing less filaments (see Table 1 andFIG. 2).

Example 13

The experiment of Example 11 was repeated, but with similar spinplatescontaining 1176 spinholes. Multifilament yarns containing 1176 filamentshaving very high tensile strength could be produced with high processingstability.

Comparative Experiment H

The experiment of Comp. Exp. F was repeated, but with the spinplatecontaining 780 spinholes; and essentially the same results.

Examples 14-16

Using the experimental set-up and conditions of Ex. 4, yarns were spunfrom a 7 mass % solution of UHPE of IV 21.4 and less than 0.3 sidegroups per 1000 per carbon atoms, with a spinrate of 1.7 g/min perspinhole. The tensile strength of the yarns obtained were somewhathigher than of comparable products made from lower molar mass UHPE.

Examples 17-20

An 8 mass % solution of UHPE having 0.65 methyl side-groups per 1000 Catoms and IV of 23 dl/g was spun into yarn, using a spinplate containing390 spinholes of geometry as in Ex. 4, but with a cone angle of 30°.Other spinning and drawing conditions were the same, but the draw ratioin the air-gap was varied. The strength of the yarns obtained iscomparable to the results with polymer containing very little propyleneas comonomer, but the creep properties are significantly improved; seeTables 1 and 2.

Comparative Experiments I-J

Analogously to Ex. 17-20 yarns were made, but with lower draw ratio inair gap and DR_(fluid), resulting in lower strength.

In FIG. 2 the tensile strengths as measured in all above experimentshave been plotted versus the logarithm of the number of filaments in therespective yarn. Also included are data points from the experimentsreported in WO 01/73173, as well as those from FIG. 1 on commercialsamples. It is clearly seen that the Examples 1-20 display higherstrength than the known yarns and yarns made in Comp. Exp. A-H, and thatthese strength values are at least 5.8*(n^(0.065)N) GPa with n at least5; which formula is represented in FIG. 2 by the bold line.

In Table 2 results of creep measurements performed on some selectedsamples at 70° C. with a load of 600 MPa are summarized. It can beconcluded that the yarns made with higher draw ratio applied to fluidfilaments, and showing higher tensile properties, also show betterresistance to creep: about 3-fold improvement in creep rate is found fora yarn made from the same polymer (Ex. 16 vs Comp. Ex. H), and about10-fold improvement for a yarn made from a UHPE polymer with smallamount of propylene as comonomer (Ex. 20).

A number of yarn samples was studied with TMDSC, results are presentedin Table 3. The various samples do not appear to show a specific trendin enthalpy effects for reversible transitions, but it can be concludedthat yarns according to the invention show higher total enthalpy valuesfor non-reversible transitions, and especially a larger peak with itsmaximum at about 152° C.

Example 29

The experiment of Example 19 was repeated, but the final drawing step onsolid filaments was now performed in two stages, by passing the yarntwice through the oven at lower rate. Instead of a final drawing stepwith DR_(solid2) of 6.4 now DR_(solid2)*DR_(solid3) of 5*1.7=8.4 wasapplied. The residence time in the oven this way increased from about 2minutes to about 6.3 minutes. The yarn obtained had a tensile strengthof 4.1 GPa, a modulus of 182 GPa, and a decalin content of 16 ppm.

Example 19 resulted in a yarn with decalin content of 135 ppm. Forcomparison, the yarn of Comp.G was found to contain about 1150 ppm ofdecalin, Comp.D 890 ppm and Comp.E 400 ppm decalin; the decrease roughlycorrelating with the decrease in filament thickness (oven residence timewas about constant).

Example 30

Example 29 was repeated, but the final solid-state 2-staged drawing stepwas now performed under an inert nitrogen atmosphere instead of in air,in order to prevent possible oxidative degradation. The yarn obtainedshowed improved tensile properties (strength 4.6 GPa and modulus 179GPa); and very low decalin content (about 18 ppm).

Example 21

The multifilament yarn of Example 13, having a titer of 930 dtex, wasused to make a uni-directional (UD) mono-layer by feeding the yarn fromseveral packages from a creel, spreading the filaments, and impregnatingthe filaments with an aqueous dispersion of Kraton® D1107stryrene-isoprene-styrene blockcopolymer as matrix material. Afterdrying the UD mono-layer had an areal density of 22.2 g/m² and a matrixcontent of about 23 mass %. Four (4) of these mono-layers of 40*40 cmsize were stacked cross-wise (fibre direction in each layer at an angleof 90° with direction in adjacent layer), a polyethylene film of about 7g/m² was placed on both sides of the stack, and the package wasconsolidated by compressing at about 110° C. and about 0.5 MPa. Theareal density of this preformed sheet was 103.8 g/m².

A number of these sheets were stacked, and the assembly was stabilizedby some stitches at each corner. The ballistic performance of theassembly was tested with 9 mm Parabellum bullets (see above). In Table 4the results are collected for assemblies with 3 different arealdensities.

Examples 22-23

Example 21 was repeated, but the mono-layers now had AD 20.2 g/m² andmatrix content 15 mass % (Ex. 22). Ex 23 was made with the yarn ofExample 11 of 465 dtex, the mono-layer had AD of 18.4 g/m² and 15 mass %of matrix. More details are given in Table 4.

Comparative Experiment K

Analogously to Ex. 21 assemblies were made from a commercialmultifilament HPPE yarn (Dyneema® SK76 1760 dtex), containing 780filaments and with TS 3.5 GPa. The mono-layer had an AD of 32.8 g/m² anda matrix content of 18 mass %.

From the data in Table 4 it is clear that the panels made with a yarnaccording to the invention show significantly better ballisticperformance in relation to their areal density. In FIG. 3 this isfurther illustrated by plotting the V50 values, the velocity at whichthe estimated probability that a bullet will perforate the panel is 50%,versus areal density for Ex. 21-23 and Comp. exp. K.

Example 24

A UD mono-layer was made as in Ex 21 with AD of 37.6 g/m² and matrixcontent of about 10 mass %. A preformed sheet was made by placing twomono-layers cross-wise with a polyethylene film of 7 g/m² on both sides,and consolidating by compression. The AD hereof was 89.2 g/m².

A number of these sheets were stacked, stabilized with stitches, andtested on anti-ballistic performance as before.

Examples 25-26

Starting from a mono-layer with AD 40.3 g/m² and 15 mass % of matrix, Ex24 was repeated.

In Ex. 26 the experiment of Ex 24 was repeated, but 4 instead of 2mono-layers were placed cross-wise and consolidated into a sheet.

Comparative Experiment L

Monolayers and sheet were made as in Comp. Exp. K. The mono-layer had anAD of 58.5 g/m² and a matrix content of 16 mass %.

The results shown in Table 4 show that also for assembled panels ofstructure differing form Ex. 21-23, the panels made from yarn accordingto the invention have significantly better protection level at the sameareal density than panels according to the state of the art. In FIG. 4this is further illustrated by plotting the V50 values versus arealdensity.

Examples 27

The mono-layers of Example 25 were made into a preformed sheet byplacing two layers cross-wise, and consolidating them analogously to theprocedure described for Example 21, but without using polyethylenefilms. Subsequently, 40*40 cm panels of varying weights were compressionmoulded from stacks of said preformed sheets, by placing a stack betweenthe heated platen of a press, compressing the stack during at least 30min. at about 6.5 MPa and at 125° C., and cooling under said pressureuntil the temperature was lower than 60° C.; the panel of 16 kg/m² wascompressed during at least 35 min. at 16.5 MPa. In Table 5 the arealdensities of the compressed panels, and the results of ballistic testingwith different ammunition are presented.

Examples 28

The mono-layers of Example 22 were made into a preformed sheet byplacing four layers cross-wise, and consolidating them without usingpolyethylene films following the procedure described before. Panels weremoulded as described for Examples 27; results of ballistic testing arecollected in Table 5.

Comparative Experiments M

Analogous to comparative experiment K a monolayer was made containingSK76 fibres and about 18 mass % of matrix, having an AD of 65.5 g/m².Preformed sheets containing 4 of said monolayers were made as before,without cover films; and panels were moulded as described for Examples27. Results are collected in Table 5.

The data of Table 5 show that panels made from the improved HPPE yarnsof the invention show also improved ballistic performance: SEA valuesare up to about 65% higher; indicating that significant weight savingsare possible while offering the same level of protection as knownpanels.

TABLE 1 Air-gap TS Modulus eab n DR_(sp) DR_(ag) (mm) DR_(fluid)DR_(solid) DR_(overall) (GPa) (GPa) (%) Ex 1 24 9 40.0 15 360 4 1440 5.2202 Ex 2 24 9 40.0 15 360 5 1800 5.3 208 comp A 24 9 15.0 15 135 5 6753.2 140 Ex 3 24 225 1.01 5 225 5 1125 5.6 203 comp B 195 9 4.4 15 40 341346 3.6 128 2.86 comp C 195 9 12 20 108 20 2160 3.7 126 3.27 Ex 4 19512.25 25.2 45 309 24.4 7532 4.3 168 3.01 Ex 5 195 12.25 33.5 50 410 25.210341 4.8 182 2.96 Ex 6 195 12.25 25.2 45 309 25.2 7779 4.5 170 3.04comp D 390 9 4.4 15 40 32 1267 3.4 126 2.82 comp E 390 9 10.2 20 92 33.63084 3.4 114 2.97 comp F 390 9 12 20 108 20 2160 3.6 121 3.24 Ex 7 39012.25 14.6 35 179 24.4 4364 3.9 162 3.07 Ex 8 390 12.25 19.4 40 238 18.94492 4.0 136 3.12 Ex 9 390 12.25 20.0 40 245 21.6 5292 4.1 157 3.07 Ex10 390 12.25 25.2 45 309 24.4 7532 4.2 166 2.98 comp G 390 12.25 2.2 1027 28 755 2.7 84 2.86 Ex 11 588 19.1 16.2 25 309 25.2 7797 4.2 155 2.98Ex 12 588 19.1 18.1 25 346 25.2 8712 4.3 153 3.05 comp H 780 9 12 20 10820 2160 3.4 114 3.23 Ex 13 1176 19.1 16.2 25 309 25.2 7797 4.1 151 3.02Ex 14 195 12.25 25.2 45 309 25.2 7779 4.6 175 3.03 Ex 15 390 12.25 20.140 246 25.2 6205 4.3 154 3.05 Ex 16 390 12.25 25.2 45 309 25.2 7779 4.5171 3.02 Ex17 390 12.25 14.6 40 179 16.2 2897 3.9 150 3.23 Ex18 39012.25 33.5 50 410 27.6 11326 4.7 178 2.91 Ex19 390 12.25 23.2 45 28427.6 7844 4.3 173 2.94 Ex20 390 12.25 22.6 45 277 26.8 7420 4.1 160 2.88comp I 390 12.25 8.8 20 108 20 2156 3.5 118 3.07 comp J 390 12.25 2.2 1027 28.1 757 2.8 96 2.74

TABLE 2 Creep test at Creep rate Creep life time 70° C./600 MPa (s⁻¹)(s) Comp. Ex. H 9.36 * 10⁻⁶ 37.8 * 10³ Ex. 16 2.93 * 10⁻⁶ 80.0 * 10³ Ex.20 0.91 * 10⁻⁶ 205.4 * 10³ 

TABLE 3 TMDSC non-reversible heat flow TMDSC reversible heat flow PeakPeak Total Peak Peak Peak Total 144° C. 152° C. Enthalpy <140° C. 144°C. 152° C. Enthalpy (J/g) (J/g) (J/g) (J/g) (J/g) (J/g) (J/g) Spectra900 190.8 0 190.8 16.6 52.5 6.4 72.6 Spectra 1000 159.9 31.0 191.0 29.731.7 10.0 71.4 Comp. F 164.3 28.7 193.0 16.2 50.1 13.9 80.2 Comp. H162.6 30.5 193.1 17.2 39.5 9.9 66.6 Ex. 10 167.6 44.2 211.8 9.3 40.314.0 63.6 Ex. 13 170.3 45.6 215.9 10.9 35.9 11.6 58.4 Ex 19 155.2 46.9202.1 9.8 49.2 16.8 75.8 Ex. 20 152.1 52.3 204.4 10.4 44.7 19.3 74.5

TABLE 4 Preformed sheet Assembled sheets number of ballistic resultsmono- AD number of AD V50 SEA layers (g/m²) sheets (kg/m²) (m/s) (J ·m²/kg) Ex. 21 4 103 20 2.0 407 322 27 2.8 456 300 33 3.4 487 280 Ex. 224 94 21 2.0 425 365 30 2.8 466 307 36 3.4 489 280 Ex. 23 4 86 23 2.0 441391 33 2.8 482 324 40 3.4 496 288 Comp. K 4 145 18 2.6 415 265 24 3.4468 258 30 4.3 493 226 Ex. 24 2 89 22 2.0 322 211 31 2.6 435 272 38 3.4466 245 Ex. 25 2 95 21 2.0 333 201 29 2.6 426 263 36 3.4 458 245 Ex. 264 176 11 2.0 375 291 16 2.6 455 296 19 3.4 501 310 Comp. L 2 131 23 3.0392 236 26 3.5 417 205 30 4.0 460 213

TABLE 5 Moulded panel Ballistic performance Areal density V50 SEA(kg/m²) Projectile (m/s) (J · m²/kg) Ex. 27 2.0 Parabellum 485 479 3.0Parabellum 502 336 3.0 FSP 583 62 4.0 FSP 615 53 16.0 AK-47 843 180 Ex.28 2.0 Parabellum 469 442 3.0 Parabellum 509 345 3.0 FSP 502 44 4.0 FSP569 45 16.0 AK-47 809 165 Comp. M 2.6 Parabellum 395 240 4.0 FSP 482 3219.0 AK-47 810 140

1. A ballistic-resistant sheet comprising: a first layer and a secondlayer each comprising high-performance polyethylene multifilament yarn;wherein the multifilament yarn comprises ultra-high molecular weightpolyethylene having an intrinsic viscosity of from about 8 dl/g to about40 dl/g as measured in decalin at 135° C. and at least 5 filaments, andhas a tensile strength of between 5.8·(n^(−0.065)) GPa and 8·n^(−0.065))GPa, wherein n is the number of filaments in the yarn; and wherein thefilaments of the multifilament yarn in the first layer and the secondlayer are spread unidirectionally within each of the layers; and whereina direction of the filaments in the first layer is rotated with respectto a direction of the filaments in the second layer.
 2. Theballistic-resistant sheet of claim 1, wherein the yarn has a tensilestrength of between 6.0·(n^(−0.065)) GPa and 8·(n^(−0.065)) GPa.
 3. Theballistic-resistant sheet of claim 1, wherein the yarn has a tensilestrength of between 6.2·(n^(−0.065)) GPa and 8·(n^(−0.065)) GPa.
 4. Theballistic-resistant sheet of claim 1, wherein the yarn has a tensilestrength of between 6.4*(n^(−0.065)) GPa and 8·(n^(−0.065)) GPa.
 5. Theballistic-resistant sheet of claim 1, wherein the yarn has a tensilestrength of between 5.8·(n^(−0.065)) GPa and 7·(n^(−0.065)) GPa.
 6. Theballistic-resistant sheet of claim 1, wherein the yarn has a tensilestrength of between 6.0·(n^(0.065)) GPa and 7·(n^(−0.065)) GPa.
 7. Theballistic-resistant sheet of claim 1, wherein the yarn has a tensilestrength of between 6.2·(n^(0.065)) GPa and 7·(n^(−0.065)) GPa.
 8. Theballistic-resistant sheet of claim 1, wherein the yarn comprises atleast 50 filaments.
 9. The ballistic-resistant sheet of claim 1, whereinthe yarn comprises at least 100 filaments.
 10. The ballistic-resistantsheet of claim 1, wherein the yarn comprises at least 200 filaments. 11.The ballistic-resistant sheet of claim 1, wherein the yarn comprisesultra-high molecular weight polyethylene having an intrinsic viscosityof from 10 dL/g to 30 dL/g as measured in decalin at 135° C.
 12. Theballistic-resistant sheet of claim 1, wherein the yarn comprisesultra-high molecular weight polyethylene having an intrinsic viscosityof from 15 dL/g to 25 dL/g as measured in decalin at 135° C.
 13. Theballistic-resistant sheet of claim 1, wherein the first and secondlayers of high-performance polyethylene multifilament yarn furthercomprise a binder, wherein the amount of binder is less than 30 mass %based on the mass of the layers.
 14. The ballistic-resistant sheet ofclaim 13, wherein the amount of binder is preferably less than 20 mass %based on the mass of the layers.
 15. The ballistic-resistant sheet ofclaim 1, further comprising a third layer and a fourth layer eachcomprising the high-performance polyethylene multifilament yarn, whereinthe filaments of the multifilament yarn in the third layer and thefourth layer are spread uni-directionally within each of the third andthe fourth layers, and wherein the direction of the filaments in eachlayer is rotated with respect to the direction of the filaments in anadjacent layer.
 16. The ballistic-resistant sheet of claim 15, whereinthe first, second, third, and fourth layers further comprise a binder,wherein the amount of binder is less than 30 mass % based on the mass ofthe layers.
 17. The ballistic-resistant sheet of claim 16, wherein theamount of binder is less than 20 mass % based on the mass of the layers.18. The ballistic-resistant sheet of claim 1, wherein the sheetcomprises polyethylene films on both sides of the sheet.
 19. Theballistic-resistant sheet of claim 1, wherein the sheet does notcomprise polyethylene films.
 20. A ballistic-resistant assemblycomprising the sheet of claim
 1. 21. The ballistic-resistant assembly ofclaim 20 having an areal density of between 1.5 kg/m² and 3.4 kg/m². 22.A ballistic-resistant assembly comprising the sheet of claim
 6. 23. Theballistic-resistant assembly of claim 22 having an areal density ofbetween 1.5 kg/m² and 3.4 kg/m².
 24. The ballistic-resistant assembly ofclaim 22 having a specific energy absorption of at least 300 J·m²/kg asmeasured against a 9·19 mm FMJ Parabellum bullet according to a testprocedure based on Stanag
 2920. 25. A ballistic-resistantcompression-molded assembly comprising the sheet of claim
 1. 26. Theballistic-resistant compression-molded assembly of claim 25 having anareal density of between 1.5 kg/m² and 16 kg/m².
 27. Theballistic-resistant compression-molded assembly of claim 25 having anareal density of between 4.0 kg/m² and 16 kg/m².
 28. Theballistic-resistant compression-molded assembly of claim 25 having aspecific energy absorption of at least 300 J·m²/kg as measured against a9·19 mm FMJ Parabellum bullet according to a test procedure based onStanag
 2920. 29. The ballistic-resistant compression-molded assembly ofclaim 25 having a specific energy absorption of at least 165 J·m²/kg asmeasured against AK-47 mild steel core bullets according to a testprocedure based on Stanag
 2920. 30. The ballistic-resistant assembly ofclaim 25 having a specific energy absorption of at least 170 J·m²/kg asmeasured against AK-47 mild steel core bullets according to a testprocedure based on Stanag 2920.